CN102781829B - Method of separating and collecting carbon nanotube and carbon nanotube - Google Patents
Method of separating and collecting carbon nanotube and carbon nanotube Download PDFInfo
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Abstract
Metallic CNTs and semiconductor CNTs are efficiently separated from a CNT mixture including the CNTs. In addition, the semiconductor CNTs are separated for each structure in good yield, in a short time, and in a simple manner using low-cost facilities by a method allowing automatic processing as well as mass processing. A plurality of columns filled with gel are connected in series. An excessive amount of CNT dispersion liquid is made to pass through the columns so that only CNTs having specific structures adhere to corresponding columns. The CNTs having different structures are separated by eluting the CNTs using eluant with high accuracy. This method allows simple and high-yield automatic processing as well as mass processing performed in a short time using low-cost facilities.
Description
Technical field
The present invention relates to and both are separated effectively from comprising the CNT (carbon nano-tube) of metal mold CNT (carbon nano-tube) with semi-conductor type CNT (carbon nano-tube) (CNT) and the CNT of semi-conductor type are carried out the method that is separated according to structure, and the CNT (carbon nano-tube) obtained thus.
Background technology
CNT has excellent character in its electrical characteristic, physical strength etc., obtains positive research and development as ultimate novel material.This CNT can utilize the various methods such as laser evaporization method, arc discharge method and chemical gas phase growth methods (CVD) to synthesize.But, under realistic situation, no matter use which kind of synthetic method, all can only obtain with the form of the mixture of metal mold CNT and semi-conductor type CNT.
In actual use, often only to use in metal mold or semi-conductor type the character of either party, therefore for being only the important topic that an urgent demand solves at top speed by the research of the CNT separation and purification of metal mold or semi-conductor type from CNT mixture.And then, in semi-conductor type CNT, because the characteristic of semi-conductor is different according to its structure (diameter, chirality (aftermentioned)), therefore strongly wish the method for obtaining the semi-conductor type CNT with uniform texture.
Although there has been the report of separating metallic CNT and semi-conductor type CNT, however all industrialization production metal mold CNT and semi-conductor type CNT in existing problems.Problem can be concluded as shown below.(1) due to through complicated operation, therefore cannot automatization; (2) need for a long time; (3) cannot process in a large number; (4) expensive equipment or medicine is needed; (5) one party in metal mold CNT and semi-conductor type CNT can only be obtained; (6) rate of recovery is low etc.
Such as, exist and will the CNT after surfactant-dispersed be utilized to carry out on microelectrode lure the dynamic method (non-patent literature 1) of electrophoresis, amine is used for method (non-patent literature 2,3) in dispersion agent in a solvent, burn the method (non-patent literature 4) etc. of semi-conductor type CNT with utilizing hydrogen peroxide selectivity, but for aforesaid method, in the middle of the problems referred to above, particularly the final material of gained is only defined as metal mold CNT, the low such problem of its rate of recovery is not resolved.
Also exist as inferior method, namely, the mixture of semi-conductor type CNT and metal mold CNT is scattered in liquid, combines with making metal mold CNT and particle selection, the metal mold CNT combined with particle is removed and isolates the method (patent documentation 1) of semi-conductor type CNT; By CNT with containing after the solution-treated of nitre ion, carry out filtering and thermal treatment and remove metal mold CNT contained in CNT, obtain the method (patent documentation 2) of semi-conductor type CNT; Use the method (patent documentation 3) of sulfuric acid and nitric acid; Apply electric field and be separated optionally mobile for CNT, obtaining the method (patent documentation 4) of the semi-conductor type CNT of constriction conductivity range.
For aforesaid method, in the middle of the problems referred to above, particularly the final material of gained is only defined as semi-conductor type CNT, the low such problem of its rate of recovery is not resolved.
To the CNT after surfactant-dispersed be utilized to utilize density gradient ultracentrifugation partition method to be separated into the method (non-patent literature 5) of metal mold CNT and semi-conductor type CNT in addition.There is following problem in the method, that is, use the very expensive instrument that ultracentrifugation separating machine is such; Ultracentrifugation lock out operation needs for a long time; There is restriction in the maximization of ultracentrifugation separating machine self; Multiple ultracentrifugation separating machine is set side by side, is difficult to carry out the process such as automatization.
Also there is the CNT-nucleic acid complex manufacturing and be made up of the CNT after being combined with nucleic acid molecule, and the method (patent documentation 5) utilizing ion exchange chromatography to carry out being separated.But, there is following problem, that is, need expensive synthetic DNA; Because separation accuracy is not too high, therefore the rate of recovery, purity are not good.
In addition, the intentional pH by the CNT solution after Adjust and use surfactant-dispersed, ionic strength, thus it is protonated to produce in various degree according to the kind of CNT, the report (patent documentation 6) metal mold is separated with semi-conductor type by applying electric field, but in the method, before separation, need to use strong acid to the pH of the nanotube mixture be suspended, ionic strength carries out the operation of pre-treatment, also have in addition implement strict process management for this reason, thus being separated (patent documentation 6 embodiment 4) of the CNT of metal mold and semi-conductor type is not finally realized.
On the other hand, about semi-conductor type CNT diameter be separated or structure be separated, also exist with above-mentioned metal mold semi-conductor type CNT be separated identical problem.
Utilize above-mentioned density gradient ultracentrifugation partition method, CNT can also be separated (non-patent literature 5) according to the difference of diameter.But, same as described above, there is following problem, that is, use very expensive instrument, need for a long time, in maximization, there is restriction, be difficult to carry out the process such as automatization.
Report the method (patent documentation 7) utilizing ion exchange chromatography above-mentioned CNT-nucleic acid complex to be isolated the structure of CNT.But, in the method, there is following problem, that is, need the CNT for each structure to prepare specific synthetic DNA, and the DNA of this synthesis be very expensive.
As previously mentioned, method in the past all cannot overcome above-mentioned problem, it is desirable to develop based on new thinking methods, from CNT the method for separating metallic CNT and semi-conductor type CNT, and isolate the method for semi-conductor type CNT of specific structure.
The present inventor etc. get down to the novel metal mold CNT different from method in the past and semi-conductor type CNT separation method, complete following invention (patent documentation 9,10,11,12).This invention, when using the combination of the dispersion agent of particular types and gel, can make semi-conductor type CNT optionally be adsorbed on gel, thus can be separated with metal mold CNT.In separation, utilize (patent documentations 11) such as electrophoresis (patent documentation 9,10), centrifugation or freezing squeezing, diffusion, infiltrations, the semi-conductor CNT be adsorbed on gel is separated with the CNT do not adsorbed.These methods not only can obtain metal mold CNT and semi-conductor type CNT both sides, and can be separated at short notice with high-recovery, and can with the equipment of cheapness, process in a large number easily, be very excellent methods.
And then, also complete the method (patent documentation 12) using suitable elutriant to reclaim the semi-conductor type CNT be adsorbed on gel.Particularly, make CNT dispersion liquid semi-conductor type CNT is adsorbed on gel, by the metal mold CNT wash-out do not adsorbed be separated through gel, reclaim the method for the semi-conductor type CNT be adsorbed on gel with elutriant and can realize reusing of gel, can also realize the automatization be separated, be very excellent method in industrial mass production metal mold semi-conductor type CNT.
In addition, also invented following method, that is, in identical method, by regulating the concentration of elutriant, thus carrying out the separation of metal mold semi-conductor type CNT, can be separated (patent documentation 12) CNT according to diameter simultaneously.The method can obtain the different CNT of diameter while metal mold CNT and semi-conductor type CNT carry out being separated, can also with high yield, short period of time, and processes in a large number with the simple equipments of cheapness, automatically process, and is very excellent method.
But, in the method, diameter be separated precision low, for obtain have uniform texture semi-conductor type CNT and need further improvement.
Patent documentation 1: Japanese Unexamined Patent Publication 2007-31238 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2005-325020 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2005-194180 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2005-104750 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2006-512276 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2005-527455 publication
Patent documentation 7: Japanese Unexamined Patent Publication 2004-142972 publication
Patent documentation 8: Japanese Unexamined Patent Publication 2006-282418 publication
Patent documentation 9: Japanese Unexamined Patent Publication 2008-285386 publication
Patent documentation 10: Japanese Unexamined Patent Publication 2008-285387 publication
Patent documentation 11: International Publication WO2009/075293 brochure
Patent documentation 12: Japanese Patent Application 2009-147557
Non-patent literature 1:Advanced Materials 18, (2006) 1468-1470
Non-patent literature 2:J.Am.Chem.Soc.127, (2005) 10287-10290
Non-patent literature 3:J.Am.Chem.Soc.128, (2006) 12239-12242
Non-patent literature 4:J.Phys.Chem.B 110, (2006) 25-29
Non-patent literature 5:Nature Nanotechnology 1, (2006) 60-65
Non-patent literature 6:Nano Letters 9, (2009) 1497-1500
Non-patent literature 7:NATURE 460, (2009) 250-253
Summary of the invention
Invent problem to be solved
The present invention completes in view of situation as above, its object is to, and provides metal mold to be separated with the CNT of semi-conductor type and by excellent for the semi-conductor type CNT precision of different structure the method be separated, and the CNT (carbon nano-tube) obtained thus.
Solve the means of problem
The present inventor etc. are studied repeatedly in order to solve the problem, and found that, by making CNT dispersion liquid significantly superfluous for a small amount of gel act on, thus can isolate the semi-conductor type CNT of single structure.And then, by after in series being linked by multiple post being filled with gel, add significantly superfluous CNT dispersion liquid, thus each post can be made to adsorb the semi-conductor type CNT of different structure, carry out Separation and Recovery (Fig. 1) once.
Usually, in order to improve separation accuracy in the separation employing post, and by below the binding capacity that sample addition is set to carrier or reduce the raising that sample size realizes separation accuracy.In the present invention, utilize and usual antipodal idea, realizing the raising of separation accuracy by specially making sample addition significantly superfluous, can be described as the novel separation method of original creation.Can think, by the middle of the diversified material existed, only make the material high relative to the affinity of carrier first combine, with remaining separating substances, thus achieve high-precision separation.
The present invention is the invention completed based on this novel opinion.
That is, according to this application, following invention can be provided.
The separation and recovery method of a <1> CNT (carbon nano-tube), it is characterized in that, act on by making the CNT (carbon nano-tube) dispersion liquid of excess quantity for the gel be filled in post, the CNT (carbon nano-tube) strong to the adsorptive power of gel is made to be adsorbed on this gel, by the solution contained the weak CNT (carbon nano-tube) of not adsorbing of the adsorptive power of above-mentioned gel, be separated with the gel being adsorbed with CNT (carbon nano-tube), gel after making elutriant act on described separation again, thus the CNT (carbon nano-tube) be adsorbed on gel is taken out.
The separation and recovery method of a <2> CNT (carbon nano-tube), it is characterized in that, be equipped with post (n >=2 of n section of having connected, n is natural number), first paragraph post is acted on by making the CNT (carbon nano-tube) dispersion liquid of excess quantity for the gel be filled in first paragraph post, until CNT (carbon nano-tube) is adsorbed on the gel of the post of n-th section, thus the CNT (carbon nano-tube) of adsorptive power intensity the first to the n-th that will be adsorbed on the gel of each post of n section, the solution separating of the CNT (carbon nano-tube) weak with the adsorptive power comprised on the gel not being adsorbed on all posts, again by making elutriant act on each post respectively, thus CNT (carbon nano-tube) different for the n kind adsorptive power be adsorbed on the gel of each post is taken out.
The separation and recovery method of the CNT (carbon nano-tube) of <3> according to <1> or <2>, it is characterized in that, the described CNT (carbon nano-tube) dispersion liquid of excess quantity for gel is the dispersion liquid of the CNT (carbon nano-tube) of amount containing the amount exceeding the CNT (carbon nano-tube) that can be adsorbed on post.
The separation and recovery method of the CNT (carbon nano-tube) of <4> according to <1> or <2>, it is characterized in that, from the gel after separation, take out the strong CNT (carbon nano-tube) with the semi-conductor of ad hoc structure of adsorptive power.
The separation and recovery method of the CNT (carbon nano-tube) of <5> according to <4>, it is characterized in that, from the gel after separation, take out the semi-conductor type CNT (carbon nano-tube) as ad hoc structure with special diameter.
The separation and recovery method of the CNT (carbon nano-tube) of <6> according to <4>, it is characterized in that, from the gel after separation, take out the semi-conductor type CNT (carbon nano-tube) as ad hoc structure with particular chiral.
The separation and recovery method of the CNT (carbon nano-tube) of <7> according to <4>, it is characterized in that, from the gel after separation, take out the semi-conductor type CNT (carbon nano-tube) as ad hoc structure with specific portion radius-of-curvature.
The separation and recovery method of the CNT (carbon nano-tube) of <8> according to <2>, it is characterized in that, the concentration that the concentration ratio making to act on the CNT (carbon nano-tube) dispersion liquid of the gel be filled in described n-th section of post acts on the CNT (carbon nano-tube) dispersion liquid of the gel be filled in described (n-1)th section of post is low.
The CNT (carbon nano-tube) that <9> mono-kind is strong to gel adsorption power, it makes the CNT (carbon nano-tube) dispersion liquid of excess quantity for the gel be filled in post described in <1> or <2> act on this gel to obtain.
<10> CNT (carbon nano-tube) be not adsorbed on gel, it utilizes the separation and recovery method of the CNT (carbon nano-tube) described in <1> or <2> to obtain.
Invention effect
According to the present invention, can, while being separated with semi-conductor type CNT by metal mold CNT, the difference of structure be utilized to be separated by semi-conductor type CNT.In addition, the material with specific structure can also be isolated from the mixture of semi-conductor type CNT equally.Except using being continuously separated of post, be also applicable to batch-type.Can the disposable semi-conductor type CNT obtaining multiple ad hoc structure accurately.As mentioned above, isolate in the method (non-patent literature 7) of the semi-conductor type CNT of single structure using expensive synthetic DNA, the CNT for each structure is needed to prepare to have the synthetic DNA of particular sequence, but in the present invention, can with identical reagent when being separated the semi-conductor type CNT of arbitrary structure, operability, cost in very excellent.In addition, equipment is also very cheap, can precision be separated excellently, and post can reuse, can also realize automatic partition from, based on these strong points, significantly can reduce separation costs.According to structure, semi-conductor type CNT can be separated, and being separated of metal mold CNT and semi-conductor type CNT can be carried out simultaneously, effective very high method can be deserved to be called.
Accompanying drawing explanation
Post in series links by Fig. 1, the explanatory view of the method for the semi-conductor type CNT of Separation and Recovery single structure.By after the post series connection that will be filled with gel is multiple, add significantly superfluous CNT dispersion liquid, thus make each post adsorb the semi-conductor type CNT of different structure.After the CNT solution containing the metal mold CNT much do not adsorbed is washed away fully, be separated each post (in right figure, frame), reclaim the CNT be adsorbed on post with elutriant.
Fig. 2 A is the optical absorption spectra (HiPco-CNT) of separating sample.
Fig. 2 B is the optical absorption spectra (HiPco-CNT) of separating sample.
Fig. 2 C is the Raman spectrum (HiPco-CNT) of separating sample.
Fig. 3 is the photo (HiPco-CNT) of separating sample.
Fig. 4 A is the result (cut before HiPco-CNT, separation) of fluorescence spectrometry.The fluorescence intensity of the wavelength of fluorescence (transverse axis) relative to excitation wavelength (longitudinal axis) is represented with isogram.Relative to saturate background, according to look bright spot, look that the order of the degree of depth of the color that the darker spot of color is such is to represent intensity grow (with reference to the scale that figure is right).Chiral index is indicated aside for main spot.
Fig. 4 B is the result (cut after HiPco-CNT, separation) of fluorescence spectrometry.The fluorescence intensity of the wavelength of fluorescence (transverse axis) relative to excitation wavelength (longitudinal axis) is represented with isogram.Relative to saturate background, according to look bright spot, look sequence list degree of the expressing strong grow (with reference to the scale that figure is right) of the degree of depth of color of the spot that color is darker.Chiral index is indicated aside for main spot.
Fig. 5 is the optical absorption spectra (CoMoCAT-CNT) of separating sample.
Fig. 6 A is the result (non-separating sample, CoMoCAT-CNT) of fluorescence spectrometry.
Fig. 6 B is the result (separating sample, CoMoCAT-CNT) of fluorescence spectrometry.
Fig. 7 is the photo (CoMoCAT-CNT) of separating sample.
Fig. 8 A is the order of chirality and the result of chiral angle of the CNT that drafting columns in series is separated.
Fig. 8 B is the order of chirality and the result of diameter of the CNT that drafting columns in series is separated.
Fig. 8 C is the order of chirality and the result of local radius of curvature of the CNT that drafting columns in series is separated.
Embodiment
Below, the present invention is described in detail.
And, in the CNT (carbon nano-tube) of Separation and Recovery " there is ad hoc structure " in the present invention, comprise following CNT (carbon nano-tube), namely, for the ad hoc structure defined with diameter, chirality, local radius of curvature and their combination etc., utilize ultraviolet-visible-near-infrared absorption spectrometry, fluorescence spectrometry, raman spectroscopy etc., with lock out operation before CNT (carbon nano-tube) contrast time clearly can identify feature based on its structure.Thus, the CNT (carbon nano-tube) with ad hoc structure after this kind of Separation and Recovery can be made up of single structure in fact certainly, also can be to extract the mixture of various structures of more than two kinds as ad hoc structure out.In addition, this kind being had the CNT (carbon nano-tube) optionally Separation and Recovery of ad hoc structure, also can be can based on the mixture of the CNT (carbon nano-tube) of other arbitrary structures measured as above containing some amounts in the scope that identifies.
The mixture that the present invention relates to comprise the mixture (hereinafter also referred to as CNT) of metal mold CNT and semi-conductor type CNT or the different semi-conductor type CNT of structure is object, is separated into the method that metal mold CNT is separated with semi-conductor type CNT and by the semi-conductor type CNT of different structure or the method be separated by the CNT of different structure.
Of the present invention is following method by the method that the CNT of different structure is separated, that is, by the CNT obtained as previously mentioned dispersion liquid is added excess quantity in the gel be filled in post, thus only by a part of CNT separation and purification strong for adsorptive power.
The excess quantity of CNT dispersion liquid mentioned here refers to more to be measured being filled in the loading capacity on the gel in post than CNT (carbon nano-tube).Namely following amount, that is, when adding the amount of the CNT put in post, the CNT ground identical with the CNT that originally cannot be adsorbed on gel that originally can be adsorbed on gel cannot be adsorbed on wash-out in post.CNT is put into after in post, cannot be adsorbed on the CNT that the gel that is filled in post is recovered puts in the new same post prepared again, when now forming the state of the CNT on the gel remaining and be adsorbed on and be filled in post, the amount putting into the CNT in post is at first exactly excess quantity.
When making the CNT dispersion liquid of excess quantity for the gel be filled in post act on, only the CNT of ad hoc structure combines, and can consider as shown below for its principle.If the CNT dispersion liquid of excess quantity is put in post for the gel be filled in post, then in the middle of various CNT, the CNT more weak than adsorptive power to the CNT with ad hoc structure that the adsorptive power of gel is strong more preferentially adsorbs, and the weak CNT of adsorptive power cannot be adsorbed on gel and be discharged.Consequently, the kind being adsorbed on the CNT on gel is restricted to the strong CNT of adsorptive power, only can obtain the CNT of particular types.
And then, if identical post is connected some sections, when adding the CNT solution of excess quantity and be separated for the gel be filled in post, then can by the disposable separation of multiple CNT different for structure.That is, the CNT with the strongest structure of adsorptive power is adsorbed on first initial post, be not adsorbed in the middle of the CNT on initial post, the CNT with the structure of the strongest adsorptive power is adsorbed on second post, thereafter so repeat, according to the order of adsorptive power power, CNT and the 3rd, the 4th, the 5th ... post combine successively, the CNT with ad hoc structure can be separated by result simultaneously.
For the CNT used in being separated, associated fabrication method, shape (diameter, length) or structure (individual layer, two layers etc.) etc. do not become problem, can as the object of separation of the present invention.
Generally speaking, the structure of CNT is defined uniquely by the chiral index formed with the group of be denoted as (n, m) 2 integers.In the present invention, said metal mold CNT and semi-conductor type CNT is the concept of CNT (carbon nano-tube) being carried out according to its electrical property classifying, the CNT (carbon nano-tube) of metal mold CNT to be chiral index be n-m=(multiples of 3), semi-conductor type CNT is defined as (n-m is not the multiple of 3) beyond it (non-patent literature 8 vegetarian rattan manage the former allusion quotation of a specified duration of Lang, a Xiao collaborate " basis of CNT (carbon nano-tube) and application " train wind shop, p13 ~ 22).
[preparation about CNT dispersion liquid]
CNT through being synthesized into forms the tens of bundles (bundle) to hundreds of comprising metal mold CNT and semi-conductor type CNT both sides usually.Metal mold CNT and semi-conductor type CNT be separated or before being separated of structure based on CNT, form the CNT of the state that every root isolates separately, carry out dispersion solubilized, it is very important for making it exist long-term and stably.
Therefore, being added with tensio-active agent as in the solution of dispersion agent by being joined by the mixture of CNT, carrying out ultrasonication fully, thus make CNT disperse isolation.Implement in the liquid of dispersion treatment at this, comprise and disperse the CNT of isolation, isolation cannot be disperseed and still form the CNT of bundle, the decolorizing carbon and metal catalyst etc. as synthesising by-product.
By utilizing separating centrifuge, the dispersion liquid obtained after ultrasonication is carried out centrifugation, thus make to be still CNT or decolorizing carbon, the metal catalyst precipitation of bundle, on the other hand, the isolated CNT defining micella with tensio-active agent can form supernatant liquor and reclaim.The supernatant liquor of gained becomes the sample used in the separation of CNT.
Solvent used in preparation as CNT dispersion liquid, most preferably is water.Consider from this point, in the preparation of CNT dispersion liquid, use water.
As tensio-active agent, any one of anion surfactant, cats product, amphoterics and nonionic surfactant can be used.
In anion surfactant, be preferably ester or dodecyl sodium sulfonate, lauroyl sarkosine, dodecylic acid, cholic acid etc. that alkyl sodium sulfate ester system and carbon number are 10 ~ 14.In amphoterics, be preferably dodecyl phosphocholine etc.These tensio-active agents can be used in combination, in addition, also can use with other tensio-active agent.
And tensio-active agent except anionic surfactant, cationic surfactant, amphoterics, nonionic surfactant, can also be the dispersion agents such as high molecular polymer, DNA, protein.For the concentration of the dispersion agents such as tensio-active agent, although different from the kind of used CNT or concentration, the kind of dispersion agent that uses etc., but such as can 0.01% ~ 25% be set in ultimate density.
Utilize the method, the concentration of the CNT in dispersion liquid can be made to become 1 μ g/ml ~ 10mg/ml, preferably become 0.1mg/ml ~ 1mg/ml.Although which kind of or its composition ratio the addition of sample be according to isolate contained in sample and become, such as, can reach several times to tens of times amount relative to the binding capacity of gel carrier.
[gel about used]
The gel used is known sugar system gel and dextran system gel (Sephacryl: allyl group dextran and N, N ' homopolymer of-methylene-bisacrylamide, GE Healthcare company), sepharose, starch gel etc. or acrylamide gel etc.In addition, also can be by the mixture of these gels, or the gel that the constituent of these gels, the mixture of other materials or compound are formed.
For gel strength, be such as preferably set to 0.01% ~ 25% in ultimate density.
Separation of the present invention is not limited to post method, such as, also go for following batch method, that is, in significantly superfluous CNT dispersion liquid, add a small amount of gel, the species adsorbs only making adsorptive power strong carries out Separation and Recovery on gel.
In the separation employing post, the liquor charging to post opens post except using, and utilizes the gravity fall of solvent to come, beyond the method for liquor charging, can also apply the method etc. utilizing pump delivery solution in airtight post.In the separation employing pump, also can promote flow velocity and process in a large number.The automatic separation employing chromatogram arrangement can also be realized.When employing the post in series linked, also can by configuring suitable valve in the front and back of post, and whole stroke automatics that will be separated.
When for bonding force is weak, be difficult to the CNT be adsorbed on gel, can by change be separated in the concentration etc. of dispersion agent of solution used improve adsorptive power, can realize thus being separated.
In order to reclaim the CNT be adsorbed on gel, the dispersion agents such as tensio-active agent can be used.
In order to calculate the ratio of metal mold CNT and semi-conductor type CNT, utilization be ultraviolet-visible-near-infrared absorption spectrometry.
Be described (Fig. 2 A, Pristine) for result when employing CNT (HiPco-CNT, the diameter 1.0 ± 0.3nm) that utilize HiPco method to synthesize.Be referred to as M
11absorbing wavelength band (about 450-650nm) caused by metal mold CNT.S
11(about more than 900nm), S
22(about 650-900nm) and S
33(about below 450nm) these 3 absorbing wavelength bands are caused by semi-conductor type CNT.Here, according to M
11with S
22the ratio of size at peak calculate the ratio of metal mold CNT and semi-conductor type CNT.Absorbing wavelength band (M
11, S
11, S
22, S
33) change according to the mean diameter of measured CNT.Diminish along with mean diameter and move to short wavelength side, become large along with mean diameter and move to long wavelength side.
In optical absorption spectra measures, the absorption of CNT is overlapped, being difficult to tell single peak is caused by single CNT, or the peak of different types of multiple CNT is formed by stacking.Therefore, in order to detect the CNT difference of each metal mold semi-conductor type, employ raman spectroscopy and measuring.Be used in sample by the HiPco-CNT before being separated, measure with the laser excitation of 633nm, result is (Fig. 2 C, Pristine).Wave number is 254,265,284,298cm-
1peak derive from semi-conductor type CNT, 197,218cm-
1peak derive from metal mold CNT.Arbitrary peak is all the CNT deriving from single structure, and the value of wave number is larger, then derive from the CNT that diameter is less.
Above-mentioned raman spectroscopy although can detect metal mold semi-conductor type CNT according to chirality, but can only obtain the information of the CNT deriving from an existing part in measuring.Although fluorescence spectrometry cannot measure metal mold CNT, but semi-conductor type CNT can be detected according to chirality difference.HiPco-CNT before being separated to be used in sample and to be measured, and result is (Fig. 4 B).To use excitation wavelength in the longitudinal axis, use wavelength of fluorescence in transverse axis, to represent with the isogram of the depth representing fluorescence intensity of color.Form spot and what show is the fluorescence of the semi-conductor type CNT deriving from single chiral.Corresponding chirality is shown in the side of spot.
Embodiment
Below, the present invention is described in detail to utilize embodiment, but the present invention is not limited.
< embodiment 1>
By adding significantly superfluous CNT sample in post, thus by the semi-conductor type CNT Separation and Recovery of single chiral.
[preparation of CNT dispersion liquid]
To in the Hipco-CNT (CNI company, the CNT utilizing chemical gas phase growth methods to synthesize, diameter 1.0 ± 0.3nm) of 100mg, add the 2%SDS aqueous solution (100ml).This solution is used blade type ultrasonic grinder (SONIFIER, BRANSON Inc., insert tip diameter: 0.5 inch), cools in cold water, simultaneously with 20W/cm
2power carry out the ultrasonication of 20 hours.After the dispersion liquid obtained utilizing ultrasonication applies ultracentrifugation separation (197,000 × g, 15 minutes), supernatant liquor is reclaimed 80%.Using this solution as CNT dispersion liquid.
The preparation of the post [be separated]
Gelled pill (Sephacryl S-300, GE Healthcare company) is employed in column support.To make the gel filled bead of mode highly reaching about 2mm in the plastic column of long 7.5cm, internal diameter 1.5cm, after passing into deionized water, balance with the 2%SDS aqueous solution.Add the CNT dispersion liquid of 5ml wherein.Then, add the 2%SDS aqueous solution, cleaning post, until solution becomes water white transparency.Gel after cleaning presents purple.By adding the 0.05%DOC aqueous solution of elutriant wherein, and the CNT be adsorbed on post is reclaimed.By the optical absorption spectra (Fig. 2 A, Col1) of the aqueous solution of gained and fluorescence spectrum (Fig. 4 B, Col1) shown in Figure 1.
[optical absorption spectra measures and fluorescence spectrometry]
For the optical absorption spectra of the CNT be made up of single structure, if semi-conductor type, then can observe S from long wavelength side
11, S
22, S
33such absorption peak, if metal mold, then can at S
22with S
33between region, observe M
11such peak.The wavelength at the peak of these absorption peaks is different according to diameter, if the CNT that diameter is large, then moves to long wavelength side, if the CNT that diameter is little, then moves to short wavelength side.The CNT synthesized is the mixture of the CNT of various kind diameter, and the peak of these mixtures of optical absorption spectra is overlapped to be observed.If the result that the optical absorption spectra of viewing Fig. 2 A measures, then can see several peak in CNT (Pristine) before separation, (Col1) through absorb-elute on post can at S
11, S
22, S
331 peak is seen in region respectively, shows the semi-conductor CNT isolating single chiral.
In optical absorption spectra, the absorption peak of other CNT is overlapping and likely cannot differentiate.Therefore, carried out the respective chirality of semi-conductor type CNT to be distinguished the fluorescence spectrometry detected.To use excitation wavelength in the longitudinal axis, use wavelength of fluorescence in transverse axis, to represent with the isogram of the depth representing fluorescence intensity of color.Form spot and what show is the fluorescence deriving from single semi-conductor CNT.Can see multiple spot (Fig. 4 A) in sample before separation, but the spectrogram of sample after being separated can only see the substantially single spot of (6,5) CNT.
Above result shows: by adding significantly superfluous CNT dispersion liquid in a small amount of gel carrier, thus can by the CNT Separation and Recovery of single chiral.
< embodiment 2>
Carry out the experiment identical with embodiment 1, by multiple post is connected, and making that the CNT of different chirality is disposable to be adsorbed on different posts, the CNT then by being adsorbed on post after being divided into each post reclaims, thus by disposable for CNT different for chirality Separation and Recovery.
The preparation of the post [be separated]
As shown in Figure 1, by 6 post series connection.Although any one in use Sephacryl S-200, Sephacryl S-300 all can be separated, but the Sephacryl S-300 that the purity employing (6,5) CNT in first, second section of post is good.In first paragraph post, be filled with the SephacrylS-300 of high 2mm, in second segment, be filled with the Sephacryl S-300 of high about 3.5mm.In the three ~ six section of post, used to make the mode highly reaching about 6mm fill Sephacryl S-200.Before separation, post is balanced with deionized water, the 2%SDS aqueous solution successively.
As the first stage, after the CNT dispersion liquid adding 5ml, the conveying 2%SDS aqueous solution and the CNT that not be adsorbed on post is removed.Thereafter, each post is separated, the CNT 0.05%DOC aqueous solution wash-out be adsorbed on each post is reclaimed (in the right frame of Fig. 1).By cut called after Col1 ~ Col6 that wash-out from the post of the first ~ six section reclaims.By post with after 2%DOC aqueous cleaning, again balance with the 2%SDS aqueous solution, for the separation of next time.In separation after second time, 6 posts linked all use Sephacryl S-200 (high 6mm).Sample former state is used in unchangeably in primary separation not to be adsorbed on post and crosses and ceaselessly CNT solution.Cut in this Separation and Recovery is set to Col7 ~ Col12 respectively.
In the stage thereafter, in secondary separation in order to can make not to be adsorbed on post crosses and ceaselessly CNT dispersion liquid be adsorbed on gel and be separated, can be separated after the concentration reducing dispersion agent.Specifically, making, ceaselessly CNT dispersion liquid utilizes ultracentrifugation be separated (197,000 × g, 3 hours) precipitation and after concentrating, dilute constant volume for 5ml, as separation sample in the mode making ultimate density become 1.5%SDS.Except post balance and do not adsorb CNT eluant in use except the 1.5%SDS aqueous solution, to be separated identical step to be separated with secondary, the post adsorbed fraction of gained is set to Col13 ~ Col18.Again being supplied in post by the CNT solution be not adsorbed on post in the separation of third time uses 1.5%SDS to be separated, and the cut of gained is set to Col19 ~ Col24.
In the phase III, cross not being adsorbed in the separation of the 4th time on post and ceaselessly CNT soln using ultracentrifugation separation (197,000 × g, 3 hours) concentrated after, dilute constant volume for 5ml, as separation sample in the mode making ultimate density become 1%SDS.Except post balance and do not adsorb CNT eluant in use except the 0.5%SDS aqueous solution, to be separated identical step to be separated with secondary, the post adsorbed fraction of gained is set to Col25 ~ Col30.The CNT solution be not adsorbed on post in the separation of the 5th time is supplied in post again and is separated, the cut of gained is set to Col31 ~ Col36.
The CNT solution be not finally combined with arbitrary post is reclaimed as metal mold CNT (Metal).
[optical absorption spectra measures and Raman measures]
The optical absorption spectra of isolated sample is shown in Fig. 2 A, B.(Pristine) before Fig. 2 A illustrates separation, be separated after metal mold CNT (Metal), the result of cut Col1 ~ Col7 that is combined with post, Fig. 2 B illustrates the result of the extracts in Col8 ~ Col31.In each cut, see different peak shape, the known structure that there occurs semi-conductor type CNT is separated.If pay close attention to S
11or S
22, then can see cut rearward then absorption peak to the trend of long wavelength side movement.In other words, there is following trend, that is, the little CNT of diameter is more promptly combined with post, and the CNT that diameter is large is just combined with post rearward.
Fig. 2 C is the result of the Raman spectrum measuring separating sample.According to the result that Raman measures, the trend that the CNT that diameter is little is promptly combined with post also can be seen, consistent with the result obtained according to optical absorption spectra.
Because optical absorption spectra is moved, therefore the color of the solution of isolated CNT is also different along with each cut.Fig. 3 is the photo of the solution of isolated each cut, and the cut of metal mold is brown, and the cut of semi-conductor type can see the change from purple to the bright-colored of green system.
[fluorescence spectrometry]
As mentioned above, utilize fluorescence spectrometry, the semi-conductor type CNT of single structure can be detected respectively, information specifically can be obtained.In Fig. 4 B, take passages the result that the cut (Col1 ~ Col31) of wash-out from each post is shown.In Col1 (6,5) CNT is split into and substantially reaches single degree, similarly as in Col4 (7,5), in Col8 (7,6), in Col16 in (8,6), Col24 in (10,2), Col29 (11,3), shown in, the CNT concentrating out particular chiral has been distinguished.If calculate the ratio of (6, the 5) CNT in Col1 cut, then reach the peak intensity of about 80%.
Above result shows: by using the post of series connection, add the CNT of excess quantity, thus can the CNT of the single chiral of Separation and Recovery any kind simultaneously.
< embodiment 3>
Use different types of CNT (CoMoCAT-CNT, Southwest Nanotechnologies company, diameter 0.8 ± 0.1nm), carry out the experiment identical with embodiment 2.As post, the post that 6 are filled with Sephacryl S-300 is conjointly used, be with the addition of the CNT dispersion liquid of 10ml.Repeat 2 circulations by employing the such separation of the 2%SDS aqueous solution in developing solvent, the CNT solution be not combined with arbitrary post is reclaimed as metal mold CNT (Metal).This CNT because diameter is little, strong to the adsorptive power of gel, therefore use the most semi-conductor CNT of 2%SDS solution absorbs.Therefore, the third time adsorption experiment reducing SDS concentration is not carried out.According to the result of optical absorption spectra, when using CoMoCAT-CNT, also can see following trend, that is, the CNT that diameter is little is adsorbed on post at first, and thicker CNT lingeringly adsorbs (Fig. 5).The result of fluorescence spectrometry is shown in Fig. 6.CoMoCAT-CNT is the sample (Fig. 6 A, non-separating sample) originally containing a lot (6,5) CNT.After being separated, the ratio of (6,5) CNT of Col1 cut reaches the peak intensity of about 85%, compared with when using HiPco-CNT in the sample, can obtain the CNT that unicity is high.For the color of solution, metal mold CNT is golden, and Col1 is thistle, and Col6 is chalybeate (Fig. 7).
According to the result of the fluorescence spectrometry of embodiment 2 and embodiment 3, by comparing of the fluorescence intensity of cut more each between each cut, the increase and decrease of the relative quantity of the CNT of each chirality can be known.Consequently, the order of the chirality be combined with post is the order ((6,5), (7,5), (8,3) ..., (8,7), (9,7)) of the transverse axis of the graphic representation of Fig. 8.In order to find out the regularity of this binding sequence, attempt drawing to various parameter.First, try to draw in chiral angle, result cannot find out regularity (Fig. 8 A).Then, draw to diameter, knot is, although there is exception, but the CNT obtaining diameter haply little is combined and separated result (Fig. 8 B) with post quickly.This result is with to utilize that optical absorption spectra measures, Raman measures the result obtained consistent.Finally, for local radius of curvature (Local Curvature radius (non-patent literature 9J.Phys.Chem.C 111, (2007) 9671-9677)) result of being drawn is (Fig. 8 C), described local radius of curvature represents the degree of crook of the key between the carbon atom defining cylindric CNT.As a result, in this case, distinguished that local radius of curvature is less and be then combined with gel more by force, local radius of curvature is larger, in conjunction with more weak, to be combined and separated with post rearward.Compared with the result of being drawn for diameter (Fig. 8 B), fluctuation is few, can obtain strong dependency.
Graphene is rolled into cylindric structure by CNT, therefore has the electronic structure similar with the electronic structure of Graphene.Identical with Graphene, in CNT, except the electronics participating in into key, do not participate in into the π-electron of key in addition, the character of this π-electron determines the character of CNT.π-electron has its electronic orbit in the direction vertical with hexagonal lattice, and in CNT, have curvature because graphene film is curling, therefore the π track of the inner side of CNT becomes large with the overlapping of the track of adjacent π-electron, and the overlap of the π-electron track outside CNT diminishes.Consequently, π-electron intention is avoided the overlap of track and the center of gravity of track is offsetted, and becomes the shape protruding outside to CNT.Now, sp
2key in conjunction with curvature (relative to sp
2the offsetting of the plane that hybridized orbital is original) large CNT (CNT that namely local radius of curvature is little), then laterally outstanding larger of π-electron track.Can think, π-electron track is to the outstanding large CNT outside CNT, then the interaction of π-electron and Sephacryl molecule is larger, therefore CNT and gel in conjunction with grow, consequently, as seen in fig. 8 c, the structure realizing CNT according to the order of the size in conjunction with radius-of-curvature is separated.
Claims (9)
1. a separation and recovery method for CNT (carbon nano-tube), is characterized in that, possesses:
Acted on by the CNT (carbon nano-tube) dispersion liquid and described gel that enable to comprise the CNT (carbon nano-tube) exceeding the amount that the gel be filled in post adsorbs, make the CNT (carbon nano-tube) strong to gel adsorption power be adsorbed on operation on this gel;
By the operation of the solution separating containing the weak CNT (carbon nano-tube) of not adsorbing of adsorptive power; With
Gel after making elutriant act on described separation, thus by operation that the CNT (carbon nano-tube) that is adsorbed on gel is taken out.
2. a separation and recovery method for CNT (carbon nano-tube), is characterized in that, possesses:
Be equipped with the post that n section of having connected is filled with gel, the gel of first paragraph post is acted on by enabling to comprise the CNT (carbon nano-tube) dispersion liquid exceeding the CNT (carbon nano-tube) being filled in the amount that the gel in first paragraph post adsorbs, until CNT (carbon nano-tube) is adsorbed on the gel of n-th section of post, thus the CNT (carbon nano-tube) of adsorptive power intensity the first to the n-th is adsorbed on the operation on the gel of each post of n section;
The operation of the solution separating of the weak CNT (carbon nano-tube) of the adsorptive power be not adsorbed on the gel of all posts will be contained; With
By making elutriant act on each post respectively, thus by the operation that CNT (carbon nano-tube) different for the n kind adsorptive power be adsorbed on the gel of each post is taken out,
Wherein, n >=2, n are natural numbers.
3. the separation and recovery method of CNT (carbon nano-tube) according to claim 1 and 2, is characterized in that,
The strong semi-conductor type CNT (carbon nano-tube) with ad hoc structure of adsorptive power is taken out from the gel after separation.
4. the separation and recovery method of CNT (carbon nano-tube) according to claim 3, is characterized in that,
The semi-conductor type CNT (carbon nano-tube) as ad hoc structure with special diameter is taken out from the gel after separation.
5. the separation and recovery method of CNT (carbon nano-tube) according to claim 3, is characterized in that,
The semi-conductor type CNT (carbon nano-tube) as ad hoc structure with particular chiral is taken out from the gel after separation.
6. the separation and recovery method of CNT (carbon nano-tube) according to claim 3, is characterized in that,
The semi-conductor type CNT (carbon nano-tube) as ad hoc structure with specific portion radius-of-curvature is taken out from the gel after separation.
7. the separation and recovery method of CNT (carbon nano-tube) according to claim 2, is characterized in that,
The concentration that the concentration ratio making to act on the CNT (carbon nano-tube) dispersion liquid of the gel be filled in described n-th section of post acts on the CNT (carbon nano-tube) dispersion liquid of the gel be filled in described (n-1)th section of post is low.
8. a CNT (carbon nano-tube) strong to gel adsorption power, it makes the CNT (carbon nano-tube) dispersion liquid of excess quantity for the gel be filled in post described in claim 1 or 2 carry out acting on obtaining.
9. be not adsorbed on the CNT (carbon nano-tube) on gel, it utilizes the separation and recovery method of the CNT (carbon nano-tube) described in claim 1 or 2 to obtain.
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| JP5663806B2 (en) * | 2010-08-06 | 2015-02-04 | 独立行政法人産業技術総合研究所 | Inexpensive separation method, separation material and separation container for carbon nanotube |
| KR101286211B1 (en) * | 2012-02-16 | 2013-07-15 | 고려대학교 산학협력단 | Method of fabricating light emitting device and light emitting device fabricated by using the same |
| CN103318868B (en) * | 2012-03-21 | 2015-07-01 | 清华大学 | Preparation method for semiconducting single-wall carbon nanotube |
| KR20150133725A (en) * | 2013-03-26 | 2015-11-30 | 고쿠리츠켄큐카이하츠호진 상교기쥬츠 소고켄큐쇼 | Separation and recovery method for carbon nanotubes having optical activity and carbon nanotubes having optical activity |
| US10046970B2 (en) | 2013-08-20 | 2018-08-14 | National Research Council Of Canada | Process for purifying semiconducting single-walled carbon nanotubes |
| WO2015077629A1 (en) | 2013-11-21 | 2015-05-28 | Atom Nanoelectronics, Inc. | Devices, structures, materials and methods for vertical light emitting transistors and light emitting displays |
| WO2015133387A1 (en) * | 2014-03-01 | 2015-09-11 | 昭和電工株式会社 | Carbon nanotube array, material, electronic appliance, process for producing carbon nanotube array, and process for producing field effect transistor |
| EP3216886A4 (en) | 2014-11-05 | 2018-04-11 | Nippon Steel & Sumitomo Metal Corporation | Hot-dip galvanized steel sheet |
| CN104692358B (en) * | 2015-02-16 | 2019-03-15 | 中国科学院物理研究所 | Carbon nanotube separation method |
| JP6456263B2 (en) * | 2015-09-02 | 2019-01-23 | 株式会社Ｎｅｘｔコロイド分散凝集技術研究所 | Method for collecting semiconducting carbon nanotubes |
| WO2017096058A1 (en) | 2015-12-01 | 2017-06-08 | LUAN, Xinning | Electron injection based vertical light emitting transistors and methods of making |
| US10541374B2 (en) * | 2016-01-04 | 2020-01-21 | Carbon Nanotube Technologies, Llc | Electronically pure single chirality semiconducting single-walled carbon nanotube for large scale electronic devices |
| CN108020573B (en) * | 2016-10-31 | 2019-12-17 | 清华大学 | Method for distinguishing carbon nanotube types |
| US10847757B2 (en) | 2017-05-04 | 2020-11-24 | Carbon Nanotube Technologies, Llc | Carbon enabled vertical organic light emitting transistors |
| US10665796B2 (en) | 2017-05-08 | 2020-05-26 | Carbon Nanotube Technologies, Llc | Manufacturing of carbon nanotube thin film transistor backplanes and display integration thereof |
| US10978640B2 (en) | 2017-05-08 | 2021-04-13 | Atom H2O, Llc | Manufacturing of carbon nanotube thin film transistor backplanes and display integration thereof |
| WO2020022414A1 (en) * | 2018-07-27 | 2020-01-30 | 国立研究開発法人産業技術総合研究所 | Aqueous solution for structural separation of carbon nanotubes, method for separating and recovering carbon nanotubes with use of said aqueous solution, and carbon nanotubes obtained by said method |
| JP6819814B1 (en) * | 2019-03-08 | 2021-01-27 | 東レ株式会社 | Carbon nanotube compositions, semiconductor devices and wireless communication devices |
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